Rapid Defect Engineering in FeCoNi/FeAl2O4 Hybrid for Enhanced Oxygen Evolution Catalysis: A Pathway to High-Performance Electrocatalysts.

Rational modulation of surface reconstruction in the oxygen evolution reaction (OER) utilizing defect engineering to form efficient catalytic activity centers is a topical interest in the field of catalysis. The introduction of point defects has been demonstrated to be an effective strategy to regulate the electronic configuration of electrocatalysts, but the influence of more complex planar defects (e.g., twins and stacking faults), on their intrinsic activity is still not fully understood. This study harnesses ultrasonic cavitation for rapid and controlled introduction of different types of defects in FeCoNi/FeAl2O4 hybrid coatings, optimizing OER catalytic activity. Theoretical calculations and experiments demonstrate that the different defects optimize the coordination environment and facilitate the activation of surface reconstruction into true catalytic activity centers at lower potentials. Moreover, it demonstrates exceptional durability, maintaining stable oxygen production at a high current density of 300 mA cm-2 for over 120 hours. This work not only presents a novel pathway for designing advanced electrocatalysts but also deepens our understanding of defect-engineered catalytic mechanisms, showcasing the potential for rapid and efficient enhancement of electrocatalytic performance.

Hybrid Metal/Spinel Oxide Coating with Microcone Arrays to Stimulate a Photothermal-Augmented Oxygen Evolution Reaction.

To boost the kinetic process of the oxygen evolution reaction (OER), hybrid CoNiFe/Fe(Fe,Mo,Al)2 O4 coatings are deposited on pure Ti substrates (namely, CoNiFe/Fe(Fe,Mo,Al)2 O4 /Ti electrodes). This new coating features a dense inner layer together with an outer layer of microcone arrays (MCAs). The electrochemical surface area of the electrodes is modulated by controlling the geometrical factors of the MCAs. For the OER in 1.0 m KOH, the electrodes require minimum overpotentials of 245 and 333 mV to realize current densities of, respectively, 10 and 100 mA cm-2 . Furthermore, the high aspect ratio of the MCAs enables the electrodes to exhibit strong sunlight capture. Under 10 min of simulated 1.0 sun illumination, the electrode's temperature can rise by up to 108.2 °C. The number of active sites and the OER reaction rate of the electrodes are further increased by photoassistance, with only 234 and 296 mV overpotentials, respectively, needed to generate current densities of 10 and 100 mA cm-2 with a Tafel slope as low as 40.9 mV dec-1 . Therefore, the application of this composite coating, which exhibits photothermal effects with respect to conventional Ti electrodes, provides an inspiration for further improvement of OER catalytic efficiency.

Enhancing Oxygen Evolution Reaction Performance in Prussian Blue Analogues: Triple-Play of Metal Exsolution, Hollow Interiors, and Anionic Regulation.

Prussian blue analogs (PBAs) are promising catalysts for green hydrogen production. However, the rational design of high-performing PBAs is challenging, which requires an in-depth understanding of the catalytic mechanism. Here FeMn@CoNi core-shell PBAs are employed as precursors, together with Se powders, in low-temperature pyrolysis in an argon atmosphere. This synthesis method enables the partial dissociation of inner FeMn PBAs that results in hollow interiors, Ni nanoparticles (NPs) exsolution to the surface, and Se incorporation onto the PBA shell. The resulting material presents ultralow oxygen evolution reaction (OER) overpotential (184 mV at 10 mA cm-2 ) and low Tafel slope (43.4 mV dec-1 ), outperforming leading-edge PBA-based electrocatalysts. The mechanism responsible for such a high OER activity is revealed, assisted by density functional theory (DFT) calculations and the surface examination before and after the OER process. The exsolved Ni NPs are found to help turn the PBAs into Se-doped core-shell metal oxyhydroxides during the OER, in which the heterojunction with Ni and the Se incorporation are combined to improve the OER kinetics. This work shows that efficient OER catalysts could be developed by using a novel synthesis method backed up by a sound understanding and control of the catalytic pathway.

Formation of Head/Tail-to-Body Charged Domain Walls by Mechanical Stress.

Domain walls (DWs) in ferroelectric materials are interfaces that separate domains with different polarizations. Charged domain walls (CDWs) and neutral domain walls are commonly classified depending on the charge state at the DWs. CDWs are particularly attractive as they are configurable elements, which can enhance field susceptibility and enable functionalities such as conductance control. However, it is difficult to achieve CDWs in practice. Here, we demonstrate that applying mechanical stress is a robust and reproducible approach to generate CDWs. By mechanical compression, CDWs with a head/tail-to-body configuration were introduced in ultrathin BaTiO3, which was revealed by in-situ transmission electron microscopy. Finite element analysis shows strong strain fluctuation in ultrathin BaTiO3 under compressive mechanical stress. Molecular dynamics simulations suggest that the strain fluctuation is a critical factor in forming CDWs. This study provides insight into ferroelectric DWs and opens a pathway to creating CDWs in ferroelectric materials.

Controlled Self-Assembly of Hollow Core-Shell FeMn/CoNi Prussian Blue Analogs with Boosted Electrocatalytic Activity.

Prussian blue analogs (PBAs) are considered as efficient catalysts for energy-related applications due to their porous nanoscale architectures containing finely disseminated active sites. Their catalytic capability can be greatly boosted by the rational design and construction of complex PBA hybrid nanostructures. However, present-day structure engineering inevitably involves additional etchant or procedure. Herein, a facile, yet controllable one-pot self-assembly strategy is introduced to prepare hierarchical core-shell polymetallic PBAs (featuring bimetallic FeMn PBAs cores and CoNi PBAs shells) with hollow nano-cages/solid nano-cube architectures. The detailed characterization of material morphology/composition, assisted with theoretical simulations, reveals the underlying formation mechanism where the key factor is the control of the nucleation rate via the use of chelating agent (citrates) and reaction kinetics. The resulting FeMn@CoNi-H compound is found to accelerate the oxygen evolution reaction activity with a low overpotential (236 mV at a current density 10 mA cm-2 ) as well as a low Tafel slope (58.4 mV dec-1 ). Such an impressive performance is endowed by the rational compositional and structural design with optimized electronic structures as well as an increase in exposed active sites. This work provides a robust, cost-effective pathway that enables chemical and morphological control in creating high-performance catalysts for water electrolysis.

A Superhydrophilic, Light/Microwave-Absorbing Coating with Remarkable Antibacterial Efficacy.

Driven by the overuse of antibiotics, pathogenic infections, dominated by the rapid emergence of antibiotic resistant bacteria, have become one of the greatest current global health challenges. Thus, there is an urgent need to explore novel strategies that integrate multiple antibacterial modes to deal with bacterial infections. In this work, a Co(Ni,Ag)/Fe(Al,Cr)2O4 composite duplex coating was fabricated using template-free sputtering deposition technology. The phase constitution of the coating was estimated to be 79 wt % Fe(Al,Cr)2O4 phase and 21 wt % of an Ag-containing metallic phase. The composite coating consisted of a ∼10 µm-thick porous outer-layer and a ∼6 µm-thick compact inner-layer, in which the outer-layer is composed of a densely stacked array of microscale cones. After exposure to ambient air for 14 days, the composite coating showed a wettability transition from a superhydrophilic nature to exhibit adhesive superhydrophobic behavior with a water contact angle of 142° ± 2.8°, but it reverted to its initial superhydrophilic state after annealing in air at 200 °C for 5 h. The absorption rate of the as-received composite coating exceeds 99% in a broad band spanning both the visible and NIR regions and showed a high photothermal efficiency to convert photon energy into heat. Similarly, the composite coating showed microwave absorption behavior with a minimum reflection loss value of 38 dB at 4.4 GHz. In vitro antibacterial tests were used to determine the antibacterial behavior of the composite coating against Escherichia coli and Staphylococcus aureus after 60 min of visible light irradiation. After this exposure, the as-prepared composite coating exhibited nearly 100% bactericidal efficiency against these bacteria. The antibacterial behavior of the coating was attributed to the synergistic effects of the superhydrophilic surface, the release of Ag+ ions, and the photothermal effect. Therefore, this composite coating may be a promising candidate to efficiently combat medical device-associated infections.

Shark teeth can resist ocean acidification.

Ocean acidification can cause dissolution of calcium carbonate minerals in biological structures of many marine organisms, which can be exacerbated by warming. However, it is still unclear whether this also affects organisms that have body parts made of calcium phosphate minerals (e.g. shark teeth), which may also be impacted by the 'corrosive' effect of acidified seawater. Thus, we examined the effect of ocean acidification and warming on the mechanical properties of shark teeth (Port Jackson shark, Heterodontus portusjacksoni), and assessed whether their mineralogical properties can be modified in response to predicted near-future seawater pH (-0.3 units) and temperature (+3°C) changes. We found that warming resulted in the production of more brittle teeth (higher elastic modulus and lower mechanical resilience) that were more vulnerable to physical damage. Yet, when combined with ocean acidification, the durability of teeth increased (i.e. less prone to physical damage due to the production of more elastic teeth) so that they did not differ from those raised under ambient conditions. The teeth were chiefly made of fluorapatite (Ca5 (PO4 )3 F), with increased fluoride content under ocean acidification that was associated with increased crystallinity. The increased precipitation of this highly insoluble mineral under ocean acidification suggests that the sharks could modulate and enhance biomineralization to produce teeth which are more resistant to corrosion. This adaptive mineralogical adjustment could allow some shark species to maintain durability and functionality of their teeth, which underpins a fundamental component of predation and sustenance of the trophic dynamics of future oceans.

Remarkable toughness of a nanostructured medium-entropy nitride compound.

A novel medium-entropy nitride (MEN) - CrCoNiN doped with Al and Ti was prepared using magnetron sputtering. The new MEN possesses a single-phase face-centered cubic (FCC) structure, offering a superior combination of hardness (∼21.2 GPa) and fracture toughness (∼4.53 MPa m1/2) that surpasses those of most of the conventional and high-entropy ceramics. The ultrahigh hardness value is attributed to a combined effect of lattice friction, solid solution, nanograin structure and compressive residual stress. The exceptional damage tolerance of the new nitride is underlain by the formation and operation of multiple steady shear bands and amorphization mediated by dislocation accumulations. The discovery of the deformation-induced amorphization and extensive shear banding in the MEN, in conjunction with the mechanistic understanding of the critical roles of high dislocation density and large lattice resistance in dislocation-mediated solid-state amorphization, opens up a new frontier for the development of damage-tolerant MPENs for application under extreme loading conditions.

Self-toughened high entropy alloy with a body-centred cubic structure.

Multiple interstitial elements (B, C and O), were incorporated into a body-centred cubic (BCC) FeMnCoCr-based interstitial high entropy alloy (iHEA). While achieving an impressive yield strength of 2.55 GPa, the new alloy also possesses appreciable ductility under mechanical loading. The unusual combination of hardening effects brought about by interstitial atoms, compositional fluctuations, and fine grain size greatly strengthened the alloy by inhibiting dislocation motion. Moreover, interstitial elements helped reinforce the grain boundaries through segregation and also assisted in tuning the phase stability. The new alloy transformed from the BCC to hexagonal closed-packed (HCP) phase initially. With increasing load the HCP phase was gradually converted into face-centred cubic (FCC); the resultant HCP/FCC nanolaminates enhanced plasticity via strain partitioning. Under higher loads, the FCC phase became dominant, giving rise to deformation twinning. Taken together, the newly developed BCC structured iHEA affords not only high strength, but also confers remarkable ductility through multiple deformation pathways.

Remarkable bactericidal traits of a metal-ceramic composite coating elated by hierarchically structured surface.

A ceramic-based coating with a hierarchical surface structure was synthesized via solid-state reaction enabled by a double cathode glow discharge technique. This innovative coating comprises two distinct layers, specifically an outer layer with a well-aligned micro-pillar array and a dense inner layer. Both are composed of a face-centered cubic Cu(Co,Ni,Fe) solid solution phase together with a spinel-type Fe(Al,Cr)2O4 oxide. This coating exhibits superhydrophobicity and, yet, a very strong adhesion to water, i.e., the so-called "rose petal effect". This coating also exhibits highly efficient antibacterial ability against both Staphylococcus aureus and Escherichia coli bacteria under both dark and visible light conditions. The excellent antibacterial property originates from the synergistic effects through the release of Cu ions coupled with photothermal activity upon light activation.

The influence of semiconducting properties of passive films on the cavitation erosion resistance of a NbN nanoceramic coating.

To alleviate the cavitation damage of metallic engineering components in hydrodynamic systems operating in marine environments, a NbN nanoceramic coating was synthesized on to a Ti-6Al-4V substrate via a double cathode glow discharge technique. The microstructure of the coating consisted of a ~13 µm thick deposition layer of a hexagonal δ'-NbN phase and a diffusion layer ~2 µm in thickness composed of face-centered cubic (fcc) B1-NaCl-structured (Ti,Nb)N. The NbN coating not only exhibited higher values of H/E and H2/E than those measured from NbN coatings deposited by other techniques, but also possessed good adhesion to the substrate. The cavitation erosion resistance of the NbN coating in a 3.5 wt% NaCl solution was investigated using an ultrasonic cavitation-induced apparatus combined with a range of electrochemical test methods. Potentiodynamic polarization measurements demonstrated that the NbN coated specimens demonstrated both a higher corrosion potential (Ecorr) and lower corrosion current density (icorr) than the uncoated substrate. Mott-Schottky analysis, combined with the point defect model (PDM), revealed that, for a given cavitation time, the donor density (ND) of the passive film on the NbN coating was reduced by 1 ~ 2 orders of magnitude relative to the uncoated Ti-6Al-4V, and the diffusivity of the point defects (D0) in the passive film grown on the NbN coating was nearly one order of magnitude lower than that on the uncoated substrate. In order to better understand the experimental observations obtained from Mott-Schottky analysis and double-charge layer capacitance measurements, first-principles density-functional theory was employed to calculate the energy of vacancy formation and the adsorption energy for chloride ions for the passive films present on both the NbN coating and bare Ti-6Al-4V.

Calcifiers can Adjust Shell Building at the Nanoscale to Resist Ocean Acidification.

Ocean acidification is considered detrimental to marine calcifiers based on laboratory studies showing that increased seawater acidity weakens their ability to build calcareous shells needed for growth and protection. In the natural environment, however, the effects of ocean acidification are subject to ecological and evolutionary processes that may allow calcifiers to buffer or reverse these short-term negative effects through adaptive mechanisms. Using marine snails inhabiting a naturally CO2 -enriched environment over multiple generations, it is discovered herein that they build more durable shells (i.e., mechanically more resilient) by adjusting the building blocks of their shells (i.e., calcium carbonate crystals), such as atomic rearrangement to reduce nanotwin thickness and increased incorporation of organic matter. However, these adaptive adjustments to future levels of ocean acidification (year 2100) are eroded at extreme CO2 concentrations, leading to construction of more fragile shells. The discovery of adaptive mechanisms of shell building at the nanoscale provides a new perspective on why some calcifiers may thrive and others collapse in acidifying oceans, and highlights the inherent adaptability that some species possess in adjusting to human-caused environmental change.

Preferentially oriented Ag-TiO2 nanotube array film: An efficient visible-light-driven photocatalyst.

Ag-TiO2 nanotube array films with the preferential orientation of crystals were fabricated on ITO glass by magnetron sputtering and anodization. Comprehensive characterization was performed to ascertain the composition and microstructure characteristics of thin films. The photocatalytic activities were evaluated through the reduction of hexavalent chromium (Cr2O72- (Cr (VI)) as a model compound under visible light irradiation. XRD and XPS studies reveal the development of preferred orientation along [001] in anatase TiO2 nanotubes by adjusting the Ag content during magnetron sputtering. Such unusual behavior is attributed to the minimization of anatase (001) surface energy assisted by Ag. The Ag-TiO2 nanotube arrays having preferred crystal orientation exhibit superior separation/transfer of photo-induced charges. Furthermore, the Ag-TiO2 nanotube arrays show improved absorption of visible light due to the SPR effect induced by Ag and the formation of heterojunction between the TNAs and Ag2O. TNA-3Ag exhibits the highest photocatalytic activities by removing 99.1 % Cr (VI) in 90 min under visible light illumination.

Insights into the antimicrobial mechanism of Ag and I incorporated ZnO nanoparticle derivatives under visible light.

ZnO nanoparticles doped with I and Ag were prepared via a solvothermal method. Characterizations of the as-synthesised samples were carried out using X-ray diffraction, X-ray photoelectron spectroscopy, UV-Vis spectrometry, Photoluminescence, transmission electron microscopy and scanning electron microscopy. The nanoparticles exhibit light absorption for wide spectra from ultra-violet (UV) to visible light. The antimicrobial efficacy was evaluated against Escherichia coli (MG1655) and Staphylococcus aureus (USA300) as models of Gram-negative and Gram-positive microorganisms, respectively. The double-doped nanoparticles demonstrated their potent efficacy against both types of microorganisms and they may have great potential in combating infectious diseases. More importantly, the insights into the mechanisms underlying the antimicrobial effects were revealed: synergistic effect of reactive oxygen species (ROS) generation and Ag+ release. Specifically, the ROS generation was believed to be dominant in the I:Ag:ZnO sample under visible light, while both ROS generation and Ag+ release were found to play an important role in the bacteria-killing by Ag:I:ZnO in the visible light and dark conditions. The Ag+ release was found to be the dominant antimicrobial mechanism for the Ag:ZnO NP sample in our experiment.

Effect of Si and C additions on the reaction mechanism and mechanical properties of FeCrNiCu high entropy alloy.

FeCrNiCu based high entropy alloy matrix composites were fabricated with addition of Si and C by vacuum electromagnetic induction melting. The primary goal of this research was to analyze the reaction mechanism, microstructure, mechanical properties at room temperature and strengthening mechanism of the composites with addition of Si and C. The reaction mechanism of powders containing (Si, Ni and C) was analyzed, only one reaction occurred (i.e., Si + C → SiC) and its activation energy is 1302.8 kJ/mol. The new composites consist of a face centered cubic (FCC) structured matrix reinforced by submicron sized SiC particles. The addition of Si and C enhances the hardness from 351.4 HV to 626.4 HV and the tensile strength from 565.5 MPa to 846.0 MPa, accompanied by a slight decrease in the plasticity. The main strengthening mechanisms of SiC/FeCrNiCu composites were discussed based on dislocation strengthening, load bearing effect, Orowan mechanism and solid solution hardening, whose contributions to the tensile strength increase are 58.6%, 6.3%, 14.3% and 20.8%, respectively.

Effect of Al alloying on cavitation erosion behavior of TaSi2 nanocrystalline coatings.

To broaden the scope of non-aerospace applications for titanium-based alloys, both hexagonal C40 binary TaSi2 and ternary Al alloyed TaSi2 nanocrystalline coatings were exploited to enhance the cavitation erosion resistance of Ti-6Al-4V alloy in acidic environments. To begin with, the roles of Al addition in influencing the structural stability and mechanical properties of hexagonal C40 Ta(Si1-xAlx)2 compounds were modelled using first-principles calculations. The calculated key parameters, such as Pugh's index (B/G ratio), Poisson's ratio, and Cauchy pressures, indicated that there was a threshold value for Al addition, below which the increase of Al content would render the Ta(Si1-xAlx)2 compounds more ductile, but above which no obvious change would occur. Subsequently, the TaSi2 and Ta(Si0.875Al0.125)2 coatings were prepared and their microstructure and phase composition were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Both the two coatings exhibited a uniform thickness of 15 µm and a densely packed structure mainly composed of spherically shaped nanocrystallites with an average diameter of about 5 nm. Nanoindentation measurements revealed that Al alloying reduced the hardness (H) and elastic modulus (E) values of the TaSi2 coating. Ultrasonic cavitation erosion tests were carried out by immersing coated and uncoated samples in a 0.5 M HCl solution. The cavitation-erosion analysis of the tested samples was investigated by various electrochemical techniques, mass loss weight and SEM observation. The results suggested that both coated samples provided a better protection for Ti-6Al-4V against the cavitation-erosion damage in acidic environments, but the addition of Al further improved the cavitation-erosion resistance of the TaSi2 coating.

How calorie-rich food could help marine calcifiers in a CO2-rich future.

Increasing carbon emissions not only enrich oceans with CO2 but also make them more acidic. This acidifying process has caused considerable concern because laboratory studies show that ocean acidification impairs calcification (or shell building) and survival of calcifiers by the end of this century. Whether this impairment in shell building also occurs in natural communities remains largely unexplored, but requires re-examination because of the recent counterintuitive finding that populations of calcifiers can be boosted by CO2 enrichment. Using natural CO2 vents, we found that ocean acidification resulted in the production of thicker, more crystalline and more mechanically resilient shells of a herbivorous gastropod, which was associated with the consumption of energy-enriched food (i.e. algae). This discovery suggests that boosted energy transfer may not only compensate for the energetic burden of ocean acidification but also enable calcifiers to build energetically costly shells that are robust to acidified conditions. We unlock a possible mechanism underlying the persistence of calcifiers in acidifying oceans.

Powder Metallurgy Synthesis of Heusler Alloys: Effects of Process Parameters.

Ni45Co5Mn40Sn10 Heusler alloy was fabricated with elemental powders, using a powder processing route of press and sinter, in place of vacuum induction melting or arc melting route. The effects of process parameters, such as compaction load, sintering time, and temperature, on the transformation characteristics and microstructures of the alloy were investigated. While the effect of compaction pressure was not significant, those of sintering time and temperature are important in causing or annulling martensitic transformation, which is characteristic of Heusler alloys. The processing condition of 1050 °C/24 h was identified to be favorable in producing ferromagnetic Heusler alloy. Longer durations of sintering resulted in an increased γ-phase fraction, which acts as an impediment to the structural transformation.

Elucidating the surface geometric design of hydrophobic Australian Eucalyptus leaves: experimental and modeling studies.

Three Australian native Eucalyptus species, i.e., Eucalyptus woodwardii, Eucalyptus pachyphylla and Eucalyptus dolorosa, were investigated, for the first time, with respect to the hydrophobicity of their leaves. It is well established that these leaves exhibit exceptionally high water repellency, in addition to an extraordinary ability to retain water, albeit their specific wetting mechanisms are still poorly understood. To identify the critical factors underlying this phenomenon, the surface topography of these leaves was subjected to micro-examination (SEM). Micro- and nanometer scale surface roughness was revealed, resembling that of the quintessential "lotus effect". Surface free energy analysis was performed on two models based on the surface topographies of the study Eucalyptus species and lotus, in order to study wetting transitions on these specific microscopic surface features. The influence of surface geometrical parameters, such as edge-to-edge distance, base radius and cylindrical height, on surface free energy with different liquid penetration depths was studied with these two models. Larger energy barriers and smaller liquid-solid contact areas were more influential in the calculations for the lotus than for Eucalyptus. The information obtained from these two models may be useful for guiding the design of novel artificial surfaces in the collection and transport of micro-volume liquids.

Enhancing the cavitation erosion resistance of D8m-Ta5Si3 nanocrystalline coatings through Al alloying.

To investigate the effects of Al alloying on the erosion-corrosion resistance of ß-Ta5Si3, both a ß-Ta5Si3 coating and an Al-alloyed ß-Ta5(Si0.83Al0.17)3 coating were synthesized on a 316 substrate by the double cathode glow discharge technique. The phase constitution, composition and microstructure of the two coatings were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The two coatings were composed of nearly rounded D8m-ß-Ta5Si3 grains with an average size of ∼4 nm, and after the addition of Al, the preferred growth orientation for the ß-Ta5Si3 coating changed from (4 0 0) to (0 0 2). The hardness, elastic modulus and contact damage resistance of the coatings were measured using a nanoindentation tester. The results showed that Al alloying improved the contact damage resistance of ß-Ta5Si3 with only a slight decrease in hardness. The erosion-corrosion behavior of the two coatings was performed in a 3.5 wt% NaCl solution containing a 12 wt% concentration of silica sand under two phase slurry flow condition and in a 3.5 wt% NaCl solution under ultrasonic cavitation erosion conditions. This revealed that the Al alloyed ß-Ta5Si3 has a higher resistance to both erosion-corrosion and ultrasonic cavitation erosion as compared to the binary ß-Ta5Si3 coating.